Method for embedding electrical and electronic circuitry

ABSTRACT

A method of protecting electrical or electronic circuitry by embedding said circuitry in a low molecular weight ethylene-alpha-olefin copolymer composition.

FIELD OF THE INVENTION

This invention relates to a method for providing a protective encasement for electrical and electronic circuitry.

BACKGROUND OF THE INVENTION

Electrical and electronic circuitry (hereinafter also identified as circuitry) is often utilized under situations such that it is subject to adverse environmental conditions and physical stress including shock and mechanical abuse as well as severe point pressure and abrasion. To eliminate or at least lessen any detrimental effect on the circuitry, the electric or electronic items are usually embedded in a protective encasement. The process of embedding is thus understood to mean generically the protection of electrical or electronic circuits or components from detrimental influences such as pressure, abrasion, moisture, oxygen, etc. Such embedding may be accomplished by casting, potting, impregnating, encapsulating, transfer molding and the like. The materials used for this purpose must have high electrical resistivity or resistance, and ought to exhibit high arc resistance and track resistance.

Polymers are commonly employed embedding materials. The preferred polymers of the prior art include polyester resins, epoxy resins, silicone rubbers, polysulfide elastomers, polyurethane elastomers, butyl rubber, moderate and high molecular weight EPDM rubber and the like.

There is a constant search for improved embedding materials that not only are pourable under application conditions but have enhanced ability to conform to intricate and, at times, minute structures. In addition, improved (lower temperature) flexibility, i.e., resistance to cracking, as well as clarity, relatively low density and thermal stability are continually being pursued.

SUMMARY OF THE INVENTION

A method of protecting electrical and electronic circuitry has been discovered wherein said circuitry is embedded in a low molecular weight ethylene-alpha-olefin copolymer composition.

DETAILED DESCRIPTION OF THE INVENTION

The instant invention relates to the discovery of a method for embedding electrical or electronic circuitry wherein a composition comprising an ethylene-alpha-olefin copolymer having a molecular weight of from about 1,000 to about 10,000 and a curative for said copolymer, is applied to said circuitry and cured.

By the term, "ethylene-alpha-olefin copolymers" is understood copolymers of ethylene with at least one monomer having the formula CH₂ CHR wherein R is C₁ -C₁₀ preferably C₁ -C₄ linear or branched alkyl, most preferably methyl. Preferably, such copolymers contain one or more non-conjugated diene such as dicyclopentadiene (DCPD), 5-ethylidene-2-norbornene, or 1,4-hexadiene. The ethylene/alpha-olefin weight ratio may range from 85/15 to 35/65, preferably 75/25 to 45/55 and most preferably 70/30 to 50/50. The amount of non-conjugated diene present in such copolymer may vary between about 0 and 35 percent, preferably 3 and 35 percent and most preferably between 5 and 20 percent, all by weight. Such ethylene-alpha-olefin copolymers are known to the art, and their preparation is disclosed in U.S. Pat. Nos. 3,819,592 (Visser et al) and 3,896,094 (Visser), which patents are herewith incorporated by reference.

The molecular weight of the copolymers ranges from about 500 to 20,000 preferably from about 1,000 to 10,000, usually from about 3,000 to 7,000.

In order to crosslink ethylene-alpha-olefin copolymers, organic (hydro) peroxides are effectively employed, and when such copolymers contain non-conjugated dienes, crosslinking may be achieved by so-called sulfur curatives.

For example, as peroxides may be used 1,1-bis(di-t-butylperoxy)-3,3,5-trimethylcyclohexane; O,O-di-t-butyl-O-(2-ethylhexyl)monoperoxy carbonate; ethyl-3,3-bis(t-butyl-peroxy)butyrate; dicumyl peroxide; benzoyl peroxide; 1,4-bis(t-butylperoxyisopropyl)benzene; 4,4,4',4'-tetra(t-butylperoxy)-2,2-dicyclohexylpropane and the like. As sulfur curatives may be mentioned, sulfur, sulfur donor compounds, accelerators, etc. such as dimethylthiuram disulfide, diphenylthiuram disulfide, dipentamethylenethiuram hexasulfide, tetramethylthiuram disulfide, zinc diethyldithiocarbamate, 4,4'-dithiodimorpholine, N,N'-dithiobis(hexahydro-2H-azepinon-2), dialkyldithiocarbamates, mercaptobenzothiazole, 4-morpholinylbenzothiazyl disulfide and others. Curatives are preferably present in the range of from about 2-20 parts per hundred parts of copolymer (phr).

Curing coagents may be incorporated in such embedding compositions for the purpose of enhancing crosslinking. Among the coagents may be mentioned 1,6-hexanediol diacrylate, lauryl methacrylate, trimethylolpropane triacrylate, ethylene dimethacrylate, 1,3-butylene dimethacrylate and the like. Curing coagents are preferably present at about 0.5-20 phr.

If so desired, the compositions of this invention may be diluted by the addition of minor amounts of aliphatic or aromatic solvents such as hexane, heptane, decane, dodecane, toluene, xylene or the like or of solvents co-reactive upon curing such as styrene, vinyl toluene, alphamethylstyrene, divinylbenzene etc.

Optionally, the embedding composition may include reinforcing or non-reinforcing fillers such as fumed or precipitated silica, aluminum trihydrate, aluminum silicates and others, preferably in the range of from about 10 to about 150 phr, provided such fillers do not detrimentally affect the electrical properties of the composition.

When cured, the embedding compositions result in solid, elastomeric materials having a tensile strength of at least 30 psi (270 kPa), usually of at least 70 psi (483 kPa) and elongation of at least 30%, generally 50% or more, preferably 70% or higher. The Shore A hardness of such cured embedding compositions may be 10 or more, usually 20 or higher. Volume resistivity of the embedding compositions should be at least 10⁹ ohms-cm, preferably 10¹¹ or higher, most preferably 10¹⁴ -10¹⁶ ohms-cm with a dielectric strength (volts/mil) of at least 200, preferably 250 or more, most preferably 400-600. The electrical dissipation factor should not be more than 0.1, preferably less than 0.05 and most preferably be in the range of 0.0001-0.01 with an arc resistance of 50-150, preferably 100-150 and most preferably 120-150, while having a dielectric constant (at 1 khz) of not more than 8, preferably 2-5, most preferably 2-3.

Compositions of this invention may be readily prepared by compounding the ethylene-alpha-olefin copolymer with the curative and any optional ingredient including antioxidants, u.v. stabilizers and the like in a suitable blender such as a two-roll open mill, internal (e.g. Banbury (trademark)) mixer, transfer mixer, homogenizer and the like.

EXAMPLE 1

Several blends were prepared for evaluation of their cured physical and electrical properties by blending the ingredients listed below in a 100 ml beaker using a spatula. After mixing, the compositions were poured into a 6"×6"×0.12" (15.24 cm×15.24 cm×0.3 cm) mold, and then placed into a press for 20 minutes at 220° F. (104.4° C.) and thereafter for 10 minutes at 360° F. (182° C.). Physical and electrical properties were then determined as indicated in Table I below.

                                      TABLE I                                      __________________________________________________________________________             Run No.                                                                        1  2   3   4   5   6  7   8   9                                        __________________________________________________________________________     EPDM-1, g                                                                              50 50  50  50  50  -- --  --  --                                       EPDM-2, g                                                                              -- --  --  --  --  50 50  50  50                                       PIDA, g 0.1                                                                               0.1 0.1 0.1 0.1 0.1                                                                               0.1 0.1 0.1                                      Peroxide-1, g                                                                          3.0                                                                               3.0 1.5 1.5 1.5 3.0                                                                               3.0 1.5 1.5                                      Co-Agent-1, g                                                                          -- --  --  5.0 5.0 -- --  5.0 5.0                                      Filler, g                                                                              -- 10  10  --  10  -- 10  --  10                                       Properties                                                                     Tensile                                                                        Strength,                                                                      psi     106                                                                               366 363 230 530 92 360 215 179                                      kPa     731                                                                               2534                                                                               2503                                                                               1586                                                                               3654                                                                               634                                                                               2482                                                                               1482                                                                               1234                                     Elongation, %                                                                          23 63  380 150 107 37 63  160 77                                       Hardness,                                                                              52 68  38  40  62  42 68  31  45                                       Shore A                                                                        __________________________________________________________________________      All compounds had a volume resistivity of 10.sup.13 ohmcm or higher.           Remarks                                                                        EPDM-1: Ethylene/propylene (E/P) = 48/52; DCPD = 9% (wt); --M.sub.v =          6550; [n] = 0.33 at 135° C. in tetralin.                                EPDM-2: E/P = 48/52; DCPD  10% (wt); --M.sub.v = 3400, [n] = 0.21              PIDA: 4,4bis(phenylisopropyl) diphenylamine, antioxidant                       Peroxide-1: 1,4bis(t-butylperoxyisopropyl) benzene (96%)                       Co-Agent-1: 1,6Hexanediol diacrylate                                           Filler: Hydrated silica                                                  

The data clearly demonstrates the wide range of physical properties attainable with the compositions of this invention while maintaining high volume resistivity.

EXAMPLE 2

Various curatives were evaluated for making cured embedding compositions using essentially the method outline above; the results are tabulated below.

                  TABLE II                                                         ______________________________________                                                Run No.                                                                        10   11     12     13   14   15   16   17                               ______________________________________                                         EPDM-1    50    50     50   50   50    50  --   --                             EPDM-3   --     --     --   --   --   --   50   50                             PIDA     0.1    0.1    0.1  0.1  0.1  0.1  0.1  0.1                            Peroxide-1                                                                              0.5    1.5    2.5  --   --   --   --   --                             Peroxide-2                                                                              --     --     --   1.5  --   --   --   --                             Peroxide-3                                                                              --     --     --   --   1.5  --   --   --                             Peroxide-4                                                                              --     --     --   --   --   1.5  --   --                             Peroxide-5                                                                              --     --     --   --   --   --   1.5  --                             Peroxide-6                                                                              --     --     --   --   --   --   --   1.5                            Properties                                                                     Tensile                                                                        Strength,                                                                      psi      119    230    204       298  214  215  147                            kPa      820    1586   1407      2055 1476 1482 1014                           Elongation,                                                                             395    150     83       250  323  260  353                            Hardness,                                                                               17     40     52        25   5*   7*   0*                             Shore A                                                                        ______________________________________                                          The volume resistivity of all experimental samples was at least 10.sup.13      ohmcm.                                                                         Remarks                                                                        Peroxide-1: See Example 1                                                      Peroxide-2: Tert. butylperoxy benzoate                                         Peroxide-3: Dicumyl peroxide                                                   Peroxide-4: 1,1bis(t-butylperoxy)-3,3,5-trimethylcyclohexane                   Peroxide-5: 0,0t-butyl-0-(2-ethylhexylmonoperoxycarbonate)                     Peroxide-6: Ethyl3,3-bis(t-butylperoxy) butyrate                               EPDM-3: E/P = 49/51; DCPD = 9% (wt); --M.sub.v = 6500                          *Samples somewhat tacky.                                                 

As is evident, a wide variety of peroxides may be utilized for carrying out the invention.

EXAMPLE 3

Following essentially the procedure disclosed in Example 1, various co-agents were evaluated for the preparation of embedding compositions. The recipes and results are summarized in Table III.

                                      TABLE III                                    __________________________________________________________________________             Run No.                                                                        18 19  20  21  22  23  24 25 26 27 28                                  __________________________________________________________________________     EPDM-1, g                                                                               50                                                                               50  50  50  50  50  50 -- -- -- --                                  EPDM-3, g                                                                              -- --  --  --  --  --  -- 50  50                                                                               50 50                                  Peroxide-1, g                                                                          1.5                                                                               1.5  1.5                                                                                1.5                                                                               1.5 1.5 1.5                                                                               1.5                                                                               1.5                                                                               1.5                                                                               1.                                  Co-Agent-1, g                                                                          2.5                                                                               5.0 10.0                                                                               20.0                                                                               --  --  -- -- -- -- --                                  Co-Agent-2, g                                                                          -- --  --  --  5.0 --  -- -- -- -- --                                  Co-Agent-3, g                                                                          -- --  --  --  --  5.0 -- -- -- -- --                                  Co-Agent-4, g                                                                          -- --  --  --  --  --  5.0                                                                               -- -- -- --                                  Co-Agent-5, g                                                                          -- --  --  --  --  --  -- 5.0                                                                               -- -- --                                  Co-Agent-6, g                                                                          -- --  --  --  --  --  -- -- 5.0                                                                               -- --                                  Co-Agent-7, g                                                                          -- --  --  --  --  --  -- -- -- 5.0                                                                               --                                  Co-Agent-8, g                                                                          -- --  --  --  --  --  -- -- -- -- 5.0                                 Properties                                                                     Tensile                                                                        Strength,                                                                      psi     141                                                                               230 399 249 263 173 133                                                                               142                                                                               102                                                                               95 166                                 kPa     972                                                                               1586                                                                               2751                                                                               1717                                                                               1813                                                                               1193                                                                               917                                                                               979                                                                               703                                                                               655                                                                               1145                                Elongation, %                                                                          210                                                                               150 113 33  97  37  50 97 127                                                                               140                                                                               93                                  Hardness,                                                                               33                                                                                40  52 72  53  62  57 34  23                                                                               22 40                                  Shore A                                                                        __________________________________________________________________________      All examples had a volume resistivity of at least 10.sup.13 ohmcm.             Remarks:                                                                       Co-Agent-1: See Example 1                                                      Co-Agent-2: Trimethylolpropane trimethacrylate                                 Co-Agent-3: N,N'--mphenylenedimaleimide                                        Co-Agent-4: Triallyl cyanurate                                                 Co-Agent-5: Trimethylolpropane triacrylate                                     Co-Agent-6: Triethyleneglycol diacrylate                                       Co-Agent-7: Lauryl acrylate                                                    Co-Agent-8: Triallyl trimellitate                                        

Coagents seemingly enhance the physical properties of invention compositions without loss of electrical properties.

EXAMPLE 4

Several monomeric, unsaturated solvents were employed with compositions of this invention following essentially the procedure described above.

Recipes and results are found in Table IV.

                  TABLE IV                                                         ______________________________________                                                   Run No.                                                                        29     30     31       32   33                                       ______________________________________                                         EPDM-1, g   50       50     50     50   50                                     PIDA, g     0.1      0.1    0.1    0.1  0.1                                    Peroxide-1, g                                                                              1.5      1.5    1.5    1.5  1.5                                    Vinyltoluene, g                                                                             5       15     --     --   --                                     Styrene, g  --       --      5     15   --                                     Alphamethyl-                                                                               --       --     --     --   10                                     styrene, g                                                                     Co-agent-1, g                                                                              --       --     --     --    5                                     Properties                                                                     Tensile Strength, g                                                                        73       529    157    517  493                                    Elongation, %                                                                              100      300    263    343  150                                    Hardness,   31       33     26     33   49                                     Shore A                                                                        ______________________________________                                          All samples exhibited volume resistivity of at least 10.sup.13 ohmcm.    

EXAMPLE 5

Certain fillers and a non-peroxide cure system were evaluated for use in embedding compositions following essentially the procedure of Example 1. For recipes and results see Table V.

                  TABLE V                                                          ______________________________________                                                    Run No.                                                                        34     35       36       37                                         ______________________________________                                         EPDM-1, g    50       50       50     50                                       PIDA, g      0.1      0.1      0.1    0.1                                      Peroxide-1, g                                                                               1.5      1.5      --     --                                       Co-Agent-1, g                                                                               5.0      5.0      --     --                                       Zinc Oxide, g                                                                               --       --       2.5    2.0                                      GMF.sup.(1), g                                                                              --       --       2.0    2.0                                      Stearic Acid, g                                                                             --       --       1.0    1.0                                      Pyrrolidone, g                                                                              --       --       2.5    --                                       Toluene, g   --       --       10     25                                       Halane.sup.(2), g                                                                           --       --       3.5    3.5                                      Filler.sup.(3), g                                                                           10       --       --     10                                       ATH.sup.(4), g                                                                              --       75       --     --                                       Properties                                                                     Tensile Strength, psi                                                                       530      345      68     196                                      kPa          3654     2379     469    1351                                     Elongation, %                                                                               107      80       863    113                                      Hardness,    62       79       11     50                                       Shore A                                                                        ______________________________________                                          All cured compositions had a volume resistivity of at least 10.sup.13          ohmcm except Run No. 37 (3.5 × 10.sup.10).                               Remarks:                                                                       .sup.(1) GMF: Parabenzoquinone dioxime                                         .sup.(2) Halane: 1,3dichloro-5,5-dimethylhydantoin                             .sup.(3) Filler: Precipitated hydrated silica                                  .sup.(4) ATH: Aluminum trihydrate                                        

EXAMPLE 6

The composition of Run No. 19 was further evaluated for its electrical properties at room temperature with these results:

Volume resistivity, ohm-cm: 10¹³

Arc Resistance, sec.: 128

Dielectric strength, V/mil: 420

Dielectric constant at 100 Hz: 2.55

Dielectric constant at 1 KHz: 2.44

Dielectric constant at 1 MHz: 2.42

Dissipation Factor at 100 Hz: 0.0050

Dissipation Factor at 1 KHz: 0.0064

Dissipation Factor at 1 MHz: 0.0084

The data points out the extraordinary suitability of the instant compositions as embedding materials.

For the purpose of embedding, an electrical overload coil having a diameter of about 5 mm, a length of 20 mm and a wire thickness of 1 mm was suspended in a 25 ml beaker by its leads. 10 g of the composition of Run No. 19 was heated to 80° C. and poured into the beaker causing the coil to be fully covered.

The whole assembly was place in a vacuum oven in order to remove any entrapped air for 10 minutes, and subsequently was exposed to 180° C. for 30 minutes in an oven.

The coil embedded by the cured elastomer was resistant to shock, moisture, mechanical abuse such as pressure and scratching without losing its original electrical characteristics.

Similar results as above are obtained using terpolymers of ethylene-propylene-1,4 hexadiene and ethylene-propylene-5-ethylidene-2-norbornene. 

What is claimed is:
 1. A method for embedding circuitry comprising:(a) applying to said circuitry a pourable composition comprising(i) an ethylene-alpha-olefin copolymer having a molecular weight of from about 500 to about 20,000; and (ii) a curative; and (b) exposing the resultant structure to curing conditions.
 2. The method of claim 1 wherein said copolymer is ethylene-propylene-non-conjugated diene terpolymer.
 3. The method of claim 2 wherein said curative is an organic peroxide or hydroperoxide.
 4. The method of claim 1 wherein said composition comprises, in addition, a coagent for said curative.
 5. The method of claim 2 wherein said non-conjugated diene is selected from the group consisting of 1,4-hexadiene, dicyclopentadiene, and 5-ethylidene-2-norbornene. 